US3721648A - Radiation-crosslinkable polymers prepared from olefinically unsaturated monomers and vinylene carbonyl monomers - Google Patents

Radiation-crosslinkable polymers prepared from olefinically unsaturated monomers and vinylene carbonyl monomers Download PDF

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Publication number
US3721648A
US3721648A US00124948A US3721648DA US3721648A US 3721648 A US3721648 A US 3721648A US 00124948 A US00124948 A US 00124948A US 3721648D A US3721648D A US 3721648DA US 3721648 A US3721648 A US 3721648A
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carbon atoms
monomers
hydrogen
alkyl
vinylene
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US00124948A
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L Mott
B Ehrig
E Muller
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2096/00—Use of specified macromolecular materials not provided for in a single one of main groups B29K2001/00 - B29K2095/00, as moulding material

Definitions

  • radiation-crosslinkable polymers can be obtained by polymerizing olefinically unsaturated monomers containing an isocyanate group, either on their own or together with other copolymerizable monomers, in the presence of compounds which form free radicals, in such a way that the isocyanate group is left intact, and converting the resulting polymers into radiation-crosslinkable substances by a polyaddition, reaction of the isocyanate groups, for example with phydroxy chalkone (cf. German Patent Specification No. 1,067,219).
  • glycidyl ethers of phenols containing light-sensitive groups such as vinylene carbonyl groups, for example the glycidyl ether of 4-hydroxychalkone
  • the polymers obtained can be crosslinked by ultraviolet radiation (cf. French Patent Specification Nos. 1,508,445 and 1,508,447).
  • this object was achieved by subjecting monomers containing (meth)acryloyloxy groups and radiation-crosslinkable vinylene carbonyl or vinylene carbonyl vinylene groups to radical polymerization in heterogeneous phase together with other radically copolymerizable monomers in such a way that the radiation-crosslinkable groups are left intact,
  • R and R may be exchanged, R represents hydrogen or methyl, R represents hydrogen, halogen (preferably chlorine), alkyl with one to four carbon atoms, aryl with six to 10 carbon atoms, or alkoxy with one to four carbon atoms, n has a value from 2 to 20,
  • m has a value from 0 to 20
  • x 0 or 1
  • R represents a group of the formula R2 7 R2 Q Q
  • R" represents a group of the formula Q
  • the monomers used in accordance with the invention can be prepared by known methods. For this purpose, an optionally nucleus-substituted monohydroxychalkone or monohydroxydibenzyl acetone compound, or a monohydroxy compound obtained from an optionally substituted naphthanlene-l-aldehyde or naphthalene-l-methyl ketone with an optionally substituted p-hydroxy-acetophenone or p-hyrooxybenzaldehyde, in solution in a suitable organic solvent, for example benzene, toluene, acetone, ethyl methyl ketone or dioxan etc., is treated with an excess, based on acid chloride, of an alkali metal hydrogen carbonate, alkali metal carbonate or alkali metal hydroxide, the reaction mixture is azeotropically dehydrated if an aqueous alkali metal hydroxide or alkali metal carbonate has been added, and acrylic
  • Hydroxyalkylation products of the abovementioned monohydroxy compounds which are to be reacted with acrylic or methacrylic acid chloride can be obtained from the monohydroxy compounds, for example phydroxyacetophenone, p-hydroxybenzaldehyde, phydroxychalkone or p-hydroxydibenzylacetone, with ethylene chlorhydrin or ethylene oxide in aqueous solution in an inert organic solvent or in the melt in the presence of an alkaline catalyst at a temperature in the range from to C..
  • hydroxalkylation products of p-hydroxyacetophenone or p-hydroxybenzaldehyde When hydroxalkylation products of p-hydroxyacetophenone or p-hydroxybenzaldehyde are prepared, they can subsequently be converted into corresponding chalkones or dibenzoylacetones by alkaline condensation with an aldehyde or an acetophenone.
  • the following monomers may be used as copolymerizable monomers in the process according to the invention:
  • esters of acrylic acid or methacrylic acid containing one to 18 carbon atoms, preferably one to eight car bon atoms, in the alcohol moiety for example methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert.-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, a butyl methacrylate isomer etc., and mixtures thereof b.
  • Aromatic vinyl or vinylidene compounds for example styrene, a halogeno styrene, or an alkyl-subv stituted styrene.
  • the alkyl group of a nuclear-alkylated styrene preferably contains orie to four carbon atoms, and an alkyl substituent on the vinyl group pereferably has one to two carbon atoms.
  • the following are specific examples of such compounds: styrene, a-methylstyrene, p-methylstyrene, p-isopropylstyrene and pchlorostyrene, preferably styrene.
  • Suitable polymerization catalysts include inorganic peroxidic compounds, such as potassium or ammonium persulphate, hydrogen peroxide and percarbonates; and organirc peroxidic compounds such as acyl peroxides, for example benzoyl peroxide, alkyl hydroperoxides such as tert.-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, dialkyl peroxides such as di-tert.-butyl peroxide, and peroxy esters such as tert.-butyl perbenzoate.
  • the inorganic or organic peroxidic compounds are advantageously used in combination with reducing agents as known per se.
  • Suitable reducing agents include, for example, sodium pyrosulphite or bisulphite, sodium formaldehyde sulphoxylate, triethanolamine, and tetraethylene pentamine.
  • the quantities in which the catalyst is used are within the limits normally employed in polymerization reactions'of this kind, e.g. from 0.01 to 5 percent by weight, based on the total quantity of monomers.
  • the conventional molecular weight regulators such as long-chain alkyl mercaptans, diisopropyl xanthogenate, nitro compounds or organic halogen compounds, may be added during the polymerization reaction.
  • the polymerization temperatures are governed both by the monomers used and also by the activation systems used, and may be preferably in the range from 0 to 150C, especially in the range from 40 to 90C.
  • copolymerization reaction on which the process according to the invention is based can be carried out either continuously or batchwise in heterogeneous phase by the known methods of emulsion, bead, suspension or precipitation polymerization as described for example in Methoden der organischen Chemie, Houben-Weyl, Vol. 14/1, 1961, pages 131-503.
  • the polymerization reaction is preferably carried out in emulsion.v
  • Suitable emulsifiers include anionic, cationic and non-ionic emulsifiers, and combinations thereof.
  • Suitable anionic emulsifiers include higher fatty acids, resin acids, acid fatty alcohol sulphuric acid esters, higher alkyl sulphonates and alkylaryl sulphonates, sulphonated castor oil, sulphosuccinic acid esters or the water-soluble salts of sulphonated ethylene oxide adducts.
  • cationic emulsifiers include salts of quaternary ammonium and pyridinium compounds.
  • non-ionic emulsifiers include the known reaction products of ethylene oxide with long-chain fatty alcohols or phenols, reaction products of more than 10 mols. of ethylene oxide with 1 mol of fatty alcohol or phenol being particularly suitable.
  • the aforementioned emulsifiers may be preferably employed in'total quantities of from 0.5 to 20 percent by weight, based on the total quantity of monomers, and especially in quantities of from 2 to 10 percent by weight.
  • the radiation-crosslinkable monomers are preferably used in quantities of from 0.1 to 5 percent by weight, based on the total quantityof monomers.
  • the copolymers obtained in accordance with the invention constitute a valuable radiation-crosslinkable product.
  • the copolymers have average molecular weights of from 15,000 to 100,000 and are soluble in organic solvents such as benzene, toluene, xylene, ethylene glycol monomethyl ether acetate etc. and, when applied to suitable substrates, such as glass, metal, wood, paper or leather, give smooth, coherent, high-gloss elastic films which, after treatment with high-energy rays, show a very high gel content, in other words are crosslinked.
  • Tl-le copolymers according to the invention are preferably obtained in the form of emulsions from which they can, if desired, be isolated as solids by precipitation with electrolytes and/or by low-temperature coagulation or by other suitable methods of isolation.
  • Radiation-induced crosslinking is carried out most effectively in thin polymer layers, so that the process according to the invention is particularly suitable for the production of high-grade crosslinked lacquer films.
  • Crosslinking can be induced by highenergy electron rays, y-rays, X-rays, ultra-violet rays, high-velocity protons, low-velocity and high-velocity neutrons, or aparticles. Ultra-violet rays are particularly suitable.
  • the polymers Before they are applied to suitable substrates for the production of films, the polymers can readily have added to them such additives as stabilizers fillers, pigments, plasticizers, levelling agents and the like.
  • a mixture of 200 g. of 4-hydroxybenzaldehyde and 200 g. of acetophenone is dissolved in 1,200 cc. of ethanol. Following the addition of a solution of 200 g. of caustic soda and 150 cc. of water, the temperature rises to 60C.. The reaction mixture is then left standing for 24 hours after which it is stirred into a solution of 1.5 liters of ice water and 500 g. of concentrated hydrochloric acid. The product is filtered under suction and washed with water until neutral. After recrystallization from ethanol, 4-hydroxychalkone melts at 186C.. The yield comprises 320 g.
  • 4-methacryloylchalkone is referred to as crosslinker I in the following Examples.
  • ethylene chlorohydrin are added dropwise with stirring at 40 to 60C., followed by heating for 4 hours at 80C..
  • the oil precipitated is washed with water and dissolved in 500 cc. of toluene, and the residual water is azeotropically distilled off.
  • EXAMPLES 1T0 3 A solution of 250 parts of water and 5 parts of a sodi-. urn salt of an alkyl sulphuric acid ester containing 10 to 16 carbon atoms and 2 percent of a monomer mixture .as indicated in the following Table, is emulsified in a reaction vessel equipped with stirring mechanism, thermometer, and reflux condenser.
  • polymerization is activated by the addition of 5.5 parts of a solution of 500 parts of water, 5 parts of potassium peroxydisulphate and 10 parts of a sodium salt of an [4'-(methacryloyloxyethoxy)-chalkone],
  • Example No. l 2 3 Comparison test butyl acrylate 59 $9 -59 60 styrene 39 39 40 39 crosslinkerl crosslinker ll crosslinker Ill
  • the polymer was separated from the dispersions obtained and dissolved in benzene.
  • the polymer solutions (40 to 50 percent were applied to glass plates treated with a release agent (silicone oil) and dried for 12 hours at 25C.
  • films based on the polymers of Examples 1 to 3 and the Comparison Test were again soluble in toluene
  • films based on the polymers of Examples l to 3 showed the following results after irradiation for 1 hour with an ultra-violet lamp (Philips HPK 125 W type 57203 B/OO): Films after drying for 1 hour at approximately 25C..
  • the gel content determined after ultra-violet irradiation is a measure of the degree of crosslinking.
  • the gel content was determined as follows:
  • the copolymerizable monomer is at least one monomer from the group consisting of acrylic or methacrylic acid esters with one to 18 carbon atoms in the alcohol moiety, styrene, a nuclear-substituted halogenostyrene, a nuclear-substituted alkyl styrene with one to four carbon atoms in the alkyl group, and a side-chain-substituted alkyl styrenes with one to two carbon atoms in the alkyl group.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00124948A 1970-03-20 1971-03-16 Radiation-crosslinkable polymers prepared from olefinically unsaturated monomers and vinylene carbonyl monomers Expired - Lifetime US3721648A (en)

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DE19702013414 DE2013414A1 (de) 1970-03-20 1970-03-20 Strahlenvernetzbare Polymerisate

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US (1) US3721648A (enrdf_load_stackoverflow)
AT (1) AT303387B (enrdf_load_stackoverflow)
BE (1) BE764554A (enrdf_load_stackoverflow)
CA (1) CA962392A (enrdf_load_stackoverflow)
DE (1) DE2013414A1 (enrdf_load_stackoverflow)
ES (1) ES389373A1 (enrdf_load_stackoverflow)
FR (1) FR2084932A5 (enrdf_load_stackoverflow)
GB (1) GB1301247A (enrdf_load_stackoverflow)
NL (1) NL7103586A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864308A (en) * 1969-06-17 1975-02-04 Agency Ind Science Techn Novel photosensitive polymer
US3896084A (en) * 1972-07-21 1975-07-22 Alexandr Ivanovich Bolshakov Copolymers of acetone with unsaturated compounds of aliphatic series and a method for preparing same
US3990958A (en) * 1972-12-22 1976-11-09 Ici Australia Limited Radiation polymerization of triallylamines using a non-polar, non-hydroxylic solvent
US5346983A (en) * 1993-05-28 1994-09-13 Hoechst Celanese Corporation Substituted phenyl compounds and processes for preparing the same
US5705539A (en) * 1995-12-11 1998-01-06 Shell Oil Company Curing polyketones with high energy radiation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000501761A (ja) * 1995-12-11 2000-02-15 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 架橋ポリケトン

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864308A (en) * 1969-06-17 1975-02-04 Agency Ind Science Techn Novel photosensitive polymer
US3896084A (en) * 1972-07-21 1975-07-22 Alexandr Ivanovich Bolshakov Copolymers of acetone with unsaturated compounds of aliphatic series and a method for preparing same
US3990958A (en) * 1972-12-22 1976-11-09 Ici Australia Limited Radiation polymerization of triallylamines using a non-polar, non-hydroxylic solvent
US5346983A (en) * 1993-05-28 1994-09-13 Hoechst Celanese Corporation Substituted phenyl compounds and processes for preparing the same
US5705539A (en) * 1995-12-11 1998-01-06 Shell Oil Company Curing polyketones with high energy radiation

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CA962392A (en) 1975-02-04
NL7103586A (enrdf_load_stackoverflow) 1971-09-22
ES389373A1 (es) 1973-06-01
DE2013414A1 (de) 1971-10-14
FR2084932A5 (enrdf_load_stackoverflow) 1971-12-17
BE764554A (fr) 1971-08-16
AT303387B (de) 1972-11-27
GB1301247A (enrdf_load_stackoverflow) 1972-12-29

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